Catalyst for synthetic methanol production



Patented Dec. 18, 1928.

JOHN c. wobbnom onovnn BLOOMEIELD, AND WILLIAM J. BANNISTER, F, 'rnnnn .PATE

NT OFFICE.

IIAUTE, INDIANA,- ASSIGNORS' T0 COMMERCIAL SOLVENTS coRPoRA'I'IoN,,; oF

TERRE HAUTE, INDIANA, A CORPORATION OF MARYLAND.

CATALYST FOR SYNTHETIC METHANOL' PRODUCTION.

No Drawing.

Our. invention relates to the production of methanol by the high pressure catalytic combination of oxides of carbon with hydrogen, and pertains more directly to the preparation of improved catalysts and their use in the may be employed, these substances reacting..-

with hydrogen according to the following equatlons I. carbon monoxide C0 2H, CH OH II. carbon dioxide CO 3H CH OH H O It is observed that when carbon dioxide is the oxide employed, one molecule of water is formed for every mtlecule of methanol produced. On the other hand when pure carbon monoxide is used, theoretically there'is nothing produced by the reaction but methanol. Actually in practice pure carbon monoxide and pure carbon dioxide are both difficult to obtain economically, so that the methanol synthesis is frequently carried out by reactinga mixture of carbon monoxide and carbon dioxide with hydrogen. Y

The production of methanol by the interaction of hydrogen and carbon oxides is essentially a hydrogenating reaction effected by hydrogenating catalysts. While the methanol reaction is ordinarily represented according to Equations I and II above, it is probable that there is an intermediate reaction and that this reaction may .involve the production of formaldehyde which is afterwards further hydrogenated to methanol, thus In the case of carbon dioxide, the first reaction occurring is, probably the reduction of that material to carbon monoxide, and Equation II may thus be expanded as follows IV. OO +H '.=H,O+ co C0 2H (EH 0 H CH OH Under certain conditions no, methanolis produced by the high pressure catalytic reaction of hydrogen and carbon monoxide-only Application filed October 25, 1926. Serial No. 144,165.

methane being formed. This reaction is illustrated by the following e uat1on:

It is, of course, certain that E uation V represents a summation ofseveral intermediate reactions. It represents the complete hydro-' genation of carbon oxide.

A possible course or react on 1s 1nd1cated' t l n I I l a v In addition to the methane reaction there are other side-reactions whlch sometimes ooour in which there are produced esters, aldehydes, organic acids, ketones, and hydrocarbons other than methane; these reactions occurring as the result of the polymerization or condensation of methanol or its decompositionproducts. I VVhe'n a gas mixture comprising carbon oxides mixed with an excess of hydrogen over the amount theoretically required to produce methanol 18 passed over a catalytic substance consisting of metals or their oxides at a pressure above 50 atmospheres and at a temperature above 25' 0.. there is nearly always produced some reaction between the gaseous components. The extent of this reaction depends to some degree on space Velocity, temperature, and pressure, but the fact remains that under the conditions outlined, carbon oxides and hydrogen react-to some extent in all cases.

The substances formed by such a process depend, both as to identity and as to amount,-

7 almost entirely .on the nature and activity of the catalytic substance present. Themeth anol catalysts mentioned in prior patents and literature are combinations of metals or their oxides whichv substances normally exert a hydrogenating catalytic died: on gas reactions. p

' The literature on the high pressure catalytic process for synthesizing methanol stat-es that the presence of nickel or any of its compounds in a catalyst. destroys or poisons the catalyst and tends to inhibit methanol forma tion. While reduced nickel is an excellent hydrogenating catalyst for many reactions, it

has been reported to react with carbon monaccording to present theories isto Cause the reaction of hydrogen and carbon oxides to produce mainly methane and. water.

We have now discovered a method of employing nickel as a methanol catalyst whereby the desirable hydrogen'ating catalytic efl'cct productive of methanol is ()l)l'2llll0(ltlll(l the tendency to methane tormation is inhibited. Briefly, our-nickel catalyst-romprises granules of nickel.- per sc. prepared by reducing nickel compounds with hydrogen at an elevated temperature.

lVe have discovered that a nickel catalyst of this type is suitable for use in the high-' pressure synthesis of methanol, all of the prior art literature notwithstanding. lVc attribute the lack of success of prior efforts to employ nickel catalysts in the synthetic methanol reaction to the character and to the degree of catalytic activity of the nickel catalyst employed. According to our own experiments, ordinary nickel catalysts such as have been employed in other. similar chemical processes are not suitable for synthetic methanol production. "We have discovered, however, that reduced nickel, prepared'by the treatment with hydrogen at elevated temperature of reducible compounds of nickel such as the hydrate, the oxide, the nit ate, or various organic salts such as the oxalate or tartrate, may form a very valuable catalyst for synthetic methanol production.

In prior attempts to adapt nickel catalysts to s nthetic methanol production a catalyst of igh activity has apparently beeiremployed and the result attained has merely been the complete hydrogenation of carbon monoxide to metlnfne, as was indicated in Equations V and VI. The nickel catalysts which were found valueless in prior art tests were composed of nickel or nickeloxide in admixture'withan inert support or in admixture with, another catalytic oxide; In case'the catalyst initially contained nickel oxide, it would, of course, be largely reduced to metallic nickel, either prior to or during use. It is a fact well-established in the catalytic hydrogenation art thatnickel reduced while in admixture with an inert supportingmass is a more active catalyst than is the identical nickel compound when reduced at the same temperature in the absence of a supportin; 'nedium. It is also well known that a reduction temperature above 300 (3., all other thingsbeing ual, produces a less active nickel catalyst t an does a lower temperature. We have found, however, that a granular reduced nickel catalyst prepared byv reaction.

providdd the proper degree of activity is imparted during the reduction.

Nickel reduced at temperatures in excess of 950 C. has little or no catalytic effect in the synthetic methanol'react-ion. \Ve attribute this fact to the character of the nickel. Reduced at so high a temperature it is too inactive a catalyst. Nickel reduced at temperatures below 300 C. is so active a catalyst that its ell'ect in the synthetic methanol reaction is to completely hydrogenate carbon monoxide-and thus to produce only methane. \Vehave discovered that nickel catalysts produced by the reduction of nickel compounds" within a temperature rzutgc of 30()S)50 (7-. may be employed in the synthetic methanol lVe have further discovered that nickel reduced within a temperature range of 50()600 C. is the best synthetic methanol catalyst.

1n the tabulation belowwve have shown Hll the results attained in the synthetic methanol process with our nickel catalysts. The process was carried out by passing a mixture of hydrogen and carbon oxide through 10 c. c. of granular nickel catalyst under-the pressures and at the temperatures indicated, the

methanol being recovered by cooling the reacted gases and condensing under pressure.- The per cent methanol in the condensate is reported and it should be understood that the residual per cent of condensate in all cases was water.

Reaction Re- Per cent duction Repressure Sm?! c. 0. concarbon of cataaction m s gfi .densate ggg gg monlyst temp. square gases per hour oxide (0.) inch in gas 300 400 3000 10,000 1.3 51.0 16.5 300 400 3000 20,000 2.2 47.5 10.5 300 400 3000 40,(X10 3.4 43. 7 l6. 5 5X) 400 3030 20, 000 4 20 16.0 500 420 3000 40, 000 3. 4 46. 5 17. 0 550 400 3000 5, 000 l. 3 78 17. 0 550 400 3000 3, 500 1. l 82 17. 0 550 400 3000 10, (XX) 2. 0 62. 9 17. 0 1550 4|!) 3000 20, (D0 3. 5 53. 9 l7. 0 550 4(1) 3000 40, 0(1) 3. 4 40. 5 17. 0 550 400 3000 B0, 000 0. 0 F0. 2 l7. 0 000 380 2000 75, 000 4. 7 45. 8 '10 600 435 2000 75, 000. 2. 7 49 16. 6 950 4(1) 3300 20. 000 l. 8 44. 3 l6. 9 950 400 3300 40,11!) 2. 5 41. 6 16. 9 950 430 3000 35, 000 2. 6 41. 0 16. Q

' Carbon dioxide replaced carbon monoxide in this test.

For the purpose of producing our improved catalysts we may employ, as a base materialpany easily-reducible compound of nickel, for example the hydrate, oxide, ni-

trate, tartrate, or oxalate. The reduction may be carried out in the ordinary manner, known to those skilled in the art, which consists in heating granules of the nickel compound to the proper temperature in a cur rent of hydrogen. The precise time required for reduction depends on the area of material vexposed and the space velocity of the hydroin the above tabulation. Nickel thus reduced below 300 C. retains a powdery character and no particle fusion is noted. The catalytic activity of such material is so great that complete hydrogenation of carbon oxides is attained. Nickel reduced within the temperature range 300-950 C. is ap arently in a state of incipient fusion such tat it has just enough catalytic activity to carry the hydrogenation of carbon monoxide to the methanol stage.

to destroy the catalytic activity in methanol work.

Granules of nickel compound suitable for reduction may be prepared by moistening the powdered or crystalline compound with water, compressing themoist mass into tablet form, and permitting it to dry slowly. In place of pure water, a dilute aqueous solution of an ag lutinating substance such as dextrinemay e employed, and better gran- .ules thus obtained.

Nickel hydrate in pure form and in dense granules highly suitable for reduction and subsequent use as a catalyst may be prepared in the following manner A solution of nickel nitratemmon eu o or similar solublenickel salt is made u in distilled water to a concentration of a ut 1%. This solution is heatedt o 95100 C. and is then treated with suflicient ammonium hydroxlde to 'ust render it alkaline, as indlcated by brilliant yellow indicator pa er.

The precipitate thus formed is allowe to by siphoning or decantation. The precipitated nickel hydroxide is separated in any convenient manner, for example b centrifuging, and is washed with about ve times Nickel reduced above 950 C. is ac-' cording to our belief so completely fused as its volume of distilled water. The precipitate is again separated, and on account of its voluminous character the final separation from the wash water is most conveniently done with a centrifuge. The moist precipitate is then spread out on plates in layersabout 1 cm. in thickness and dried at 100-105 C. for about 10-15 hours. The precipitate forms hard dense cakes during the drying period, and is subsequently broken up into granules of a size suitable for catalytic use.

It is understood however, that the specific example of the method of preparing nickel hydrate for reduction and subsequent use as a methanol catalyst is illustrative merely. Other nickel compounds may be used as the basis of a reduced nickel cata1yst as was disclosed in a prior section of this specification.

While in the above tabulation of the results obtained in the production of synthetic methanol with our nickel catalysts, the reaction temperatures employed vary from' 380-430 0., it should be understood that these catalysts are operative throughout the entire operative range of reaction temperature' for synthetic methanol production-that is 250-450 C.

Now having described our invention, we claim the following as new and novel 1. A process for the production of synthetic methanol which comprises passing a 7 mixture of hydrogen and carbon oxides at a pressure in excess. of 50 atmospheres and at a temperature of 250450 C. over a catalyst containing nickel reduced at a temperature of 300950 C.

2. A process for the production of synthetic methanol which comprises passing a mixture of hydrogen and carbon oxides at a pressure in excess of 50 atmospheres and at a temperature of 250-450 C. over a catalyst containing nickel reduced at a temperature of '500-600 C.

'3. A process for the production of synthetic methanol which comprises passing a mixture ofhydrogen and carbon oxides at a pressure in excess of 50 atmospheres and at a temperature of 380430 C. over a catalyst containing nickel reduced at a temperature i of 500600 C. settle and the supernatant liquor is removed In testimony whereof we aflix our signa- WILLIAM J. BANNISTER 

